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Title: Effects of Anion Identity and Concentration on Electrochemical Reduction of CO 2

Abstract

The electrochemical reduction of CO 2 is known to be influenced by the concentration and identity of the anionic species in the electrolyte; however, a full understanding of this phenomenon has not been developed. Here, we present the results of experimental and computational studies aimed at understanding the role of electrolyte anions on the reduction of CO 2 over Cu surfaces. Experimental studies were performed to show the effects of bicarbonate buffer concentration and the composition of other buffering anions on the partial currents of the major products formed by reduction of CO 2 over Cu. It was demonstrated that the composition and concentration of electrolyte anions has relatively little effect on the formation of CO, HCOO -, C 2H 4, and CH 3CH 2OH, but has a significant effect on the formation of H 2 and CH 4. Continuum modeling was used to assess the effects of buffering anions on the pH at the electrode surface. The influence of pH on the activity of Cu for producing H 2 and CH 4 was also considered. Changes in the pH near the electrode surface were insufficient to explain the differences in activity and selectivity observed with changes in anion bufferingmore » capacity observed for the formation of H 2 and CH 4. Therefore, it is proposed that these differences are the result of the ability of buffering anions to donate hydrogen directly to the electrode surface and in competition with water. The effectiveness of buffering anions to serve as hydrogen donors is found to increase with decreasing p K a of the buffering anion.« less

Authors:
 [1];  [2];  [1];  [1];  [1]
  1. Department of Chemical Engineering, University of California, Berkeley, CA 94720, Joint Center for Artificial Photosynthesis, Material Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
  2. Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, Joint Center for Artificial Photosynthesis, Material Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1420191
Grant/Contract Number:  
SC0004993; DGE-0802270; AC02-05CH11231
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Name: ChemElectroChem Journal Volume: 5 Journal Issue: 7; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
Germany
Language:
English

Citation Formats

Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, and Bell, Alexis T. Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2. Germany: N. p., 2018. Web. doi:10.1002/celc.201701316.
Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, & Bell, Alexis T. Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2. Germany. doi:10.1002/celc.201701316.
Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, and Bell, Alexis T. Mon . "Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2". Germany. doi:10.1002/celc.201701316.
@article{osti_1420191,
title = {Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2},
author = {Resasco, Joaquin and Lum, Yanwei and Clark, Ezra and Zeledon, Jose Zamora and Bell, Alexis T.},
abstractNote = {The electrochemical reduction of CO2 is known to be influenced by the concentration and identity of the anionic species in the electrolyte; however, a full understanding of this phenomenon has not been developed. Here, we present the results of experimental and computational studies aimed at understanding the role of electrolyte anions on the reduction of CO2 over Cu surfaces. Experimental studies were performed to show the effects of bicarbonate buffer concentration and the composition of other buffering anions on the partial currents of the major products formed by reduction of CO2 over Cu. It was demonstrated that the composition and concentration of electrolyte anions has relatively little effect on the formation of CO, HCOO-, C2H4, and CH3CH2OH, but has a significant effect on the formation of H2 and CH4. Continuum modeling was used to assess the effects of buffering anions on the pH at the electrode surface. The influence of pH on the activity of Cu for producing H2 and CH4 was also considered. Changes in the pH near the electrode surface were insufficient to explain the differences in activity and selectivity observed with changes in anion buffering capacity observed for the formation of H2 and CH4. Therefore, it is proposed that these differences are the result of the ability of buffering anions to donate hydrogen directly to the electrode surface and in competition with water. The effectiveness of buffering anions to serve as hydrogen donors is found to increase with decreasing pKa of the buffering anion.},
doi = {10.1002/celc.201701316},
journal = {ChemElectroChem},
number = 7,
volume = 5,
place = {Germany},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1002/celc.201701316

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Cited by: 16 works
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